Copper-Catalyzed General and Selective α-C(sp³)–H Silylation of Amides via 1,5-Hydrogen Atom Transfer

ACS Catalysis, Год журнала: 2024, Номер 14(3), С. 1725 - 1732

Опубликована: Янв. 18, 2024

The development of a general and selective method for α-C(sp3)–H silylation feedstock amines has been long-standing challenge. In this paper, we disclose mild, general, practical, highly regio- diastereoselective various readily available acyclic, cyclic, aromatic with silylboranes through copper-catalyzed intramolecular 1,5-hydrogen atom transfer (HAT) strategy. mild activation 2-iodobenzamide to generate an aryl radical enabled by ligand-coordinated silyl copper complex without additional heating or photoinduced conditions, as well the 1,5-HAT process produce crucial α-aminoalkyl species, is key success chemistry. This protocol demonstrated its potential utility in late-stage modification structurally drugs bioactive molecules. Therefore, it expected that will find applications synthetic chemistry drug discovery.

Язык: Английский

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Copper-Catalyzed Radical Relay 1,3-Carbocarbonylation across Two Distinct C═C Bonds

Organic Letters, Год журнала: 2024, Номер 26(15), С. 3014 - 3019

Опубликована: Март 28, 2024

The radical relay provides an effective paradigm for intermolecular assembly to achieve functionalization across remote chemical bonds. Herein, we report the first 1,3-carbocarbonylation of α-carbonyl alkyl bromides two separate C═C reaction is highly chemo- and regioselective, with C(sp3)–C(sp3) bonds one C═O bond formed in a single orchestrated operation. In addition, synthesis method under mild conditions using inexpensive copper as catalyst allows facile access structurally diverse products. plausible mechanism investigated through series control experiments, including trapping, clock critical intermediate 18O labeling experiment.

Язык: Английский

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Photoinduced Copper-Catalyzed Regio- and Enantioselective Alkynylation of Epoxides

ACS Catalysis, Год журнала: 2024, Номер 14(10), С. 7553 - 7561

Опубликована: Май 1, 2024

Epoxides are privileged and valuable electrophiles frequently utilized as versatile building blocks in synthetic chemistry to prepare diverse alcohols through ring-opening reactions. However, the catalytic stereoconvergent cross-coupling of racemic epoxides with electro- or nucleophiles has remained a persistent challenge. In this work, we present mild method achieve regio- enantioselective alkynylation various alkynes, resulting synthesis β-chiral homopropargyl via photoinduced copper-based system. The use monofluoro-substituted non-C2 symmetric bisoxazoline diphenylamine ligand played pivotal role success chemistry, its distinct electronic steric effects proving crucial enhancing both reactivity stereoselectivity. Mechanistic studies supported idea that reaction underwent regioselective nucleophilic iodides, followed by radical alkynes. Notably, hydroxyl group generated from epoxide may play an auxiliary achieving high enantioselectivity.

Язык: Английский

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Access to Versatile Functionalized Cu(III) Complexes Enabled by Direct Transmetalation to Well‐Defined Copper(III) Fluoride Complex Me₄N⁺[Cu(CF₃)₃F]^‐

Chinese Journal of Chemistry, Год журнала: 2024, Номер 42(10), С. 1107 - 1113

Опубликована: Янв. 30, 2024

Comprehensive Summary The invention of a well‐defined Cu(III) fluoride complex Me 4 N + [Cu(CF 3 ) (F)] ‐ 1 enabled to access versatile functionalized complexes [Me N] [Cu(X)(CF ] (X = C 6 F 5 , C≡C, CN, Cl, t BuOO, SCN, OAc, SAr), many them for the first time. availability these allowed us evaluate trans ‐influence order ligand in complexes: Bn > CF – py ~ CH C≡C NO 2 PhO BuOO COO .

Язык: Английский

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Ring‐Opening Functionalization/Cyclization Reactions of Cycloalkanols under Transition‐Metal‐Free Conditions

European Journal of Organic Chemistry, Год журнала: 2024, Номер 27(9)

Опубликована: Фев. 8, 2024

Abstract Cycloalkanols ring‐opening transformation is one of the most valuable and wide area research. Among numerous methods that have been developed, transition‐metal‐free approaches attracted great interest from both chemists pharmacologists. This largely due to advantages being environmentally benign, cost‐effective operationally simple. Here we provide a comprehensive outline on recent advances in synthesis distally substituted ketones cyclic compounds via cycloalkanols under conditions.

Язык: Английский

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Diversified Synthesis of All-Carbon Quaternary gem-Difluorinated Cyclopropanes via Copper-Catalyzed Cross-Coupling

Organic Letters, Год журнала: 2023, Номер 25(15), С. 2674 - 2679

Опубликована: Апрель 11, 2023

The construction of all-carbon quaternary centers in small-ring systems is important but challenging organic synthesis. Herein, by taking gem-difluorocyclopropyl bromides (DFCBs) as a type general and versatile building block, we developed practical method for gem-difluorinated cyclopropanes (DFCs). reaction relies on the involvement radical intermediate, which can couple with wide range nucleophiles under copper catalysis.

Язык: Английский

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A General Copper‐Box System for the Asymmetric Arylative Functionalization of Benzylic, Propargylic or Allenylic Radicals

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Июль 27, 2024

Abstract Radical‐involved arylative cross‐coupling reactions have recently emerged as an attractive strategy to access valuable aryl‐substituted motifs. However, there still exist several challenges such limited scope of radical precursors/acceptors, and lack general asymmetric catalytic systems, especially regarding the multicomponent variants. Herein, we reported a copper‐Box system for three‐component vinylarenes 1,3‐enynes, with oxime carbonates aryl boronic acids. The proceed under practical conditions in absence or presence visible‐light irradiation, affording chiral 1,1‐diarylalkanes, benzylic alkynes allenes good enantioselectivities. Mechanistic studies imply that copper/Box complexes play dual role both generation ensuing cross‐coupling. In cases irradiation could improve activity complex toward initial generation, enabling better efficiency match between formation

Язык: Английский

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Boryl Radical-Mediated Halogen-Atom Transfer (XAT) Enables the Sonogashira-Like Alkynylation of Alkyl Halides

Chemical Science, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

The Sonogashira-like alkynylation of alkyl halides is achieved by a photocatalytic approach exploiting amine-ligated boryl radicals as halogen-atom transfer mediators in combination with alkynyl sulfones SOMOphilic reagents.

Язык: Английский

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Cobalt-catalyzed reductive alkynylation to construct C(sp)-C(sp3) and C(sp)-C(sp2) bonds

Chinese Chemical Letters, Год журнала: 2023, Номер 35(7), С. 109283 - 109283

Опубликована: Ноя. 9, 2023

Язык: Английский

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Decarboxylative cyanation and thiocyanation via catalytic electron donor-acceptor complex with copper catalysis

Science China Chemistry, Год журнала: 2024, Номер 67(9), С. 3019 - 3028

Опубликована: Авг. 12, 2024

Язык: Английский

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